Hydroxy hydrocarbon n-substituted dialkylene triamines



United States Patent 3,200,153 HYDROXY HYDROCARBON N-SUBSTITUTED DIALKYLENE TRIAMINES Willard H. Kirkpatrick, Sugar Land, and Virgil L. Scale, Houston, Tex, assignors to Nalco Chemical Company, Chicago, 111., a corporation of Delaware No Drawing. Filed Mar. 26, 1962, Ser. No. 182,615 1 Claim. (Cl. 260570.6)

This invention, in general, relates to dialkylene triamines which are N-substituted with at least one Z-hydroxypropyl-l group and at least one hydroxy hydrocarbon group having 4-12 carbons.

This application is a continuation-in-part application of our copending application Serial No. 69,300, filed November 15, 1960, and now Patent No. 3,152,188, issued October 6, 1964, which application'is a continuation-inpart of our earlier copending application Serial No. 614; 048, filed October 5, 1956, now abandoned.

One of the objects of the invention is to provide new and useful N-substituted dialkylene triarnines having N- substituted monohydroxy hydrocarbon radicals of monohydric hydrocarbon compounds of two types-predominantly hydrophilic and predominantly hydrophobic.

Another object is to provide N-substituted dialkylene triamines having N-substituted alkanol radicals of three carbons and N-substituted monohydroxy hydrocarbon radicals of monohydroxy hydrocarbon compounds which are predominantly hydrophobic in nature.

In accordance with the invention, new chemical compounds which are, broadly speaking, dialkylene triarnines which are N-substituted with (a) at least one 2-hydroxypropyl-l group which is predominantly hydrophilic, and (b) at least one monohydroxy hydrocarbon radical having more than three carbons and up to 12 carbons of monohydric hydrocarbon compositions such as the hydrolysis products of 2-methyl propylene oxide-1,2; butylene oxide-1,2; butylene oxide-2,3; styrene oxide; epoxy diisobutylene in its various isomeric forms; epoxy tri isobutylene in its various isomeric forms; and other hydrocarbon epoxides' having at least four carbons such as the epoxidized isomers of hexene, monoepoxides of butadiene, isoprene, etc., including those which are available as mixtures and mixed isomers.

Our compounds may be derived by reacting dialkylene triamines with two different types of hydrocarbon epoxides having the oxygen in an oxirane ring. Propylene oxide-1,2 provides N-substituted hydroxy alkyl radicals with a secondary hydroxyl group in the hydroxyl propyl radical (CH -8HCHa) B;- The hydrocarbon epoxides of group (b), above, give N- substituted hydroxy hydrocarbon radicals of at least four carbons with a non-primary, in general a secondary, hy-

droxyl group. While in theory, some oxides might give radicals with tertiary hydroxyl groups, we have no evi- V deuce to confirm either the presence or absence of such groups.

3,200,153 Patented Aug. 10, 1965 The dialkylene triamines contemplated within the scope of the invention include diethylenetriamine, dipropylene- 1,3 or 1,2-triamine whose alkylene groups are and higher dialkylene triamines with up to six carbons per alkylene groups, e.g., bis-(hexamethylene) triarnine,

also called dihexamethylene triamine.

The compositions contemplated by the present invention range from dialkylene triamines which are substituted by only.one radical of each of the two types of hydroxy hydrocarbon groups, discussed supra, to dialkylene triamines which are completely N-substituted by both of the foregoing types of hydroxy hydrocarbon groups.

In general, the compositions fall within the formula:

wherein R is a lower alkylene radical of 26 carbons; R R R R R are selected from the group consisting of hydrogen and monohydroxy hydrocarbon radicals of at least three carbons, at least one of R R R R and R being 2-hydroxypropyl and at least one other of R R R R and R being a monohydroxy hydrocarbon radical of at least four carbons.

Propylene oxide-1,2 and styrene oxide are well known hydrocarbon expoxides. Bu-tylene oxide is usually available as a mixture of butylene oxide-1,2 and buty lene oxide-2,3. Epoxidized diisobutylene and epoxidized triisobutylene in their isomeric forms, the epoxidized isomers of hexene, and the monoepoxides of butadiene are not as well known. The method of preparing the latter hydrocarbon epoxides comprises oxidation of the corresponding unsaturated hydrocarbons with peracetic acid, preferably containing little or no acetic acid. The unsaturated hydrocarbon and the peracetic acid are agitated while the reaction mixture is held at a low temperature, preferably around room temperature or below. In many instances it is important that little or no acetic acid be present in the original peracetic acid because the produced epoxides readily react with acetic acid to form undesirable by-products.

Diisobutylene exists in two isomeric forms, one having the double bond in the 1,2 position, the other having the double bond in the 2,3 position. These isomers have boiling points differing only about 3 C. and hence cannot be separated with any high degree of efiiciency. However, the oxirane derivatives of these isomers having boiling point differences of about 10 C. and can be effectively separated by the usual distillation rocedures. The epoxide of the a isomer of diisobutylene is 1,2- epoxy-2,4,4-trimethyl pentane. This isomer has a high reactivity with amines, resembling the reactivity of styrene oxide. It has a specific gravity, '20/20 0, of 0.823; a boiling point (760 mm.) of 141 C.; a viscosity at 20 C. of 1.21 cps. and a refractive index, in; at 20 C., of 1.4097. The epoxide of the 8 isomer of diisobutylene, 2,3-epoxy-2,4,4-t-rimethyl pentane, has a relatively low reactivity in comparison to the epoxide of the a isomer. The epoxide of the B isomer of diisobutylene has a specific gravity, 20/20 C., of 0.814; a boiling point (750 mm.) of 128 C.; a viscosity at 20 C. of 0.9 2; and a refractive index, 11 at 20 C, of 1.4026.

One method of preparing the compositions is to react a mixture of hydrocarbon epoxides of the two types such as a mixture of propylene oxide-1;2 with one or.rnore hydrocarbon epoxides of group containing at least 4 carbons. A more preferred procedure from the standpoint of obtaining reproducible results is the sequential addition of one type of hydrocarbon epoxide and then the other. In some instances it will be desirable to react only a portion of one type with one primary amino group, then react the other primary amino group with the other type of hydrocarbon epoxide and thereafter add the remainder of the first-mentioned type. Other manipulative steps will be suggested to one skilled in the art, depending upon the type of composition desired.

The hydrocarbon epoxides and dialkylene triamines are reacted by mixing the compositions, usually under pressure, at elevated temperatures. The hydrocarbon epoxide may be in the gaseous phase or the liquid phase depending upon the boiling point of the hydrocarbon epoxide at the reaction pressure and temperature. An initial temperature of approximately 75-90 C. is recommended for gaseous oxides, e.g., propylene oxide-1,2, the reaction temperature being held below 120 C. during the reaction period. These temperatures are raised somewhat for the higher molecular weight oxides, particularly those which are more inert to reaction with amines than the gaseous oxides, e.g., propylene oxide-1,2. Only the monoepoxy hydrocarbon compounds are employed in this invention because polyepoxy hydrocarbon compounds lead to polymerization and often to crosslinking to form an insoluble resinous composition. Basic alkali metal compounds should be excluded because they promote polyoxyalkylation.

The following general example illustrates the general procedure for preparing the compositions of our invention:

General example The dialkylene tri-amine is weighed and charged into an oxyalkylation reaction vessel. By means of a mechanical pump the triamine is cycled through ,the reactor until a temperature of approximately 75-150 C. is secured, depending upon the reactivity of the particularly hydrocarbon epoxide to be added. Then the hydrocarbon epoxide is slowly added, maintaining circulation under pressure until an exothermic reaction begins to occur. The rate of addition is controlled in order to maintain a temperature preferably between 90 C. and 200 C., once again depending on the reactivity of the particular hydrocarbon epoxide, at a pressure preferably above atmospheric. External cooling is applied to hold the reaction temperature in the range desired. After the desired amount of oxide has been added, the mixture is recycled for one-half to one hour or more to react all of the oxide.

The following examples illustrate the specific embodiments of the invention.

Example I One mol of diethylene triamine is heated in an oxyalkylation reactor to approximately 85 C. At that point propylene oxide-1,2 is added slowly until an exothermic reaction begins. The rate of addition is controlled to maintain a temperature of about 120 C. and a pressure of 50 p.s.i. After one mol of propylene oxide-1,2 has been added, which requires approximately two hours, the mixture is recycled for 30 minutes.

Thereafter two mols of a mixture of butylene oxide-1,2 and butylene oxide-2,3 are added at a temperature of about 110 C. in a manner similar to the addition of propylene oxide-1,2, above. The reaction temperature is held at about 140 C. and the mixture is recycled for onehalf hour after all of the butylene oxide has been added. The resulting composition is 2-hydroxypropyl-1, di(hydroxy butyl) diethylene triamine.

Example 11 One mol of diethylene triamine and one mol of propylene oxide-1,2 are reacted according to the procedure outlined in Example I for reaction of propylene oxide and diethylene triamine. Thereafter, two mols of liquid styrene oxide are reacted under pressure at a temperature not exceeding 150 C.recycling the mixture for an additional hour after all of the styrene oxide is added. Thereafter an additional mol of propylene oxide 1,2 is reacted under similar conditions to the foregoing. The resulting product is di-(hydroxy propyl), di(phenyl hydroxy ethyl) diethylene triamine.

Example III Propylene oxide-1,2 and diethylene triamine are reacted at a molar ratio of 1:1 according to the procedure of Example I. Thereafter, the resultant composition is reacted with 4 mols of the epoxide of the isomer of diisobutylene at an initial reaction temperature of about 110 C. at a pressure in excess of atmospheric. The reaction temperature is held below 150 C. while the oxide is added in small increments. After all of the oxide is added, the reactants are recycled for a period of one and one-half to two hours at a temperature of about 140 C. The resulting product is 2-hydroxypropyl, tetra-(2,4,4 trimethyl-hydroxypentyl)-diethylene triamine.

Example IV Three mols of a mixture of the epoxidized isomers of triisobutylene are reacted with one mol of diethylene triamine at an initial reaction temperature of 120 C. in an oxyalkylation reactor according to the procedure outlined in the general example. The reaction temperature is maintained between ISO-155 C. while the oxide is added. After all of the oxide has been added the mixture is recycled at a temperature of 150 C. for one and one-half to two hours. Thereafter, one mol of propylene oxide-1,2 is added to the reaction product under the temperature and pressure conditions outlined in Example I.

Example V One mol of propylene oxide-1,2 and one mol of dipropylene-1,2-triamine are reacted according to the procedure outlined in Example I for the reaction of propylene oxide-1,2 and diethylene triamine. Thereafter two mols Example VI One mol of dipropylene-1,3-triarnine and one mol of propylene oxide-1,2 are reacted according to the procedure outlined in the general example. The propylene oxide-1,2 is added slowly to the polyamine at an initial temperature of C. The reaction temperature is maintained between to C. while the oxide is added. After all of the oxide is added the mixture is recycled for a period of one hour at a temperature of 110 C. Thereafter two mols of a mixture of the epoxides of mixed hexene isomers are slowly added to the reaction product at an initial temperature of C. The reaction temperature is maintained at -155 C. while the oxide mixture is added. After all of the oxide mixture is added the reactants are recycled for one and one-half hours at C. The resulting product is 2-hydroxy propyl, di- (hydr-oxy hexyl) dipropylene triamine.

Example VII One mol of diethylene triamine and one mol of butylene oxide-1,4 are reacted according to the procedure of the general example at an initial temperature of 105 C. and at a reaction temperature of 115-120 C. After all of the oxide is added the mixture is recycled for one hour at 115 C. Thereafter 4 mols of propylene oxide-1,2 are reacted with the reaction product under the conditions outlined in Example I for the reaction of propylene oxidel,2 and diethylene t-riamine. The resulting product is hydroxy butyl, tetra(2-hydroxypropyl) diethylene triamine.

Example VIII Into a jacketed pressure reaction vessel are charged 105 parts by weight of technical grade dihexamethylene triamine. Into a separate charge vessel are charged 2.9 parts by weight of propylene oxide-1,2. The charge vessel is connected to the reaction vessel by means of suitable pipe connections. The reactor contents are thoroughly purged with purified natural gas while heating the reactor contents by means of the steam jacket until a temperature of approximately 70 C. is reached. Heating is continued until 100 C. is reached. At 100 C., the propylene oxide-1,2 is pressured into the reactor by means of purified natural gas at a rate sufficient to give a controlled exothermic reaction. The propylene oxide-1,2 addition is continued until the charge vessel supply is depleted, the reactor temperature being maintained at 100-120 C. After all the propylene oxide-1,2 has been added to the reactor, the reactor contents are recycled for one hour at 100-120 C. to yield the one mol propylene oxide-1,2 adduct. Then 3.5 parts of butylene oxide-1,2 are reacted with the propylene oxide-1,2 adduct in the conditions specified in Example VII for the butylene oxide reaction to give N-Z-hydroxypropyl, N-2-hydroxybutyl dihexamethylene triamine.

Example IX Repeating the technique described in Example VIII,

but reacting 10.5 parts by weight of technical dihexamethylene triamine with 5.8 parts by weight of propylene oxide-1,2 to yield the two mol propylene oxide-1,2 adduct, there is produced hydroxybutyl, di-((2-hydroxypropyl) dihexamethylene triamine.

It will be seen from the foregoing description that the invention herein described is adapted to produce a wide variety of compositions. One of the advantages of this invention lies in adaptability in producing a wide variety of polar compounds. The 2-hydroxypropyl group has a greater affinity to water and provides a greater polarity in the compositions than the monohydroxy hydrocarbon groups having at least four carbons. By varying the number of each type of hydroxy hydrocarbon group and its position in the molecule, we are able to produce a wide variety of compositions of widely different polarities. Furthermore, the variability of polarities of these compositions is further enhanced by being able to choose from a group of different compounds of each type of hydrocarbon oxide as a reactant. Still further, We are able to leave some of the amine groups unreacted for the favorable properties which the free amino groups impart such as corrosion inhibition of ferrous metals.

For purposes of providing greatest differences in polarities between the N-hydroxy hydrocarbon groups, we prefer that the groups containing 4-12 carbons be those with 6-12 carbons, i.e., those provided by styrene oxide, epoxidized diisobutylene, epoxidized triisobutylcne, and epoxidized hexene, e.g., 2-phenyl-2-hydroxyethyl, hydroxy hexyl, Z-hydroxy-2,4,4-trimethylpentyl-l, 3-hydroxy-2,4,4- trimethylpentyl-Z, and hydroxy-triisobutylene-yl.

The compounds prepared in accordance with the invention are suitable for use as intermediates for various types of organic syntheses, for resin formation, in detergent manufacture, and for the preparation of emulsifiers. The compounds of the present invention can also be employed as starting materials for oxyalkylation reactions in which long chains composed of oxyalkylene groups are added to the hydroxyl groups of such starting materials. Thus, by reacting with the compounds of the examples in the presence of an alkaline catalyst such as sodium hydroxide or sodium methylate with 1,2-propylene oxide, long chains can be built up on the terminal hydroxyl groups to give compositions having a molecular weight of 1200 to 4000 attributable to oxypropylene groups. These compounds can be employed in proportions of 1 part of said compound to from 2000 to 50,000 parts of a water-in-oil petroleum emulsion for the purpose of breaking such emulsion and effecting separation of the water from the oil.

The invention is hereby claimed as follows:

A compound having the formula wherein R is a lower alkylene radical of 26 carbons, one of R R R R and R is Z-hydroxypropyl, another of R R R R and R is a member selected from the group consisting of 2-phenyl-Z-hydroxyethyl, mono-secondaryhydroxyhexyl, Z-hydroxy-2,4,4-trimethylpentyl-l, 3-hydroxy-2,4,4-trimethylpentyl-2, and hydroxy-triisobutylcnyl, and the remainder of R R R R and R independently are selected from the group consisting of said member, hydrogen, and 2-hydroxypropyl.

References Cited by the Examiner UNITED STATES PATENTS 2,617,675 12/57 Hofer et a1 260--584 2,884,459 4/59 Kirkpatrick et a1. 260584 2,901,461 8/59 Auerbach et a1. 260563 2,944,030 7/60 Patton 260-584 CHARLES B. PARKER, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,200,153

Willard H. Kirkpatrick et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 6, line 48, for "2,617,675" read 2,817,675

Signed and sealed this 8th day of March 1966.

(SEAL) Attest:

ERNEST W. SWIDER Attesting Officer EDWARD J. BRENNER Commissioner of Patents August 10 196 

